DE1622916A1 - Color photographic material - Google Patents

Description

AGFA-GEVAERTAQ

PATENT DEPARTMENT U Νβ

LEVERKUSEN

15th min 1968

Color photographic material

The invention relates to a material photographic material for the silver dye bleaching process that contains azo dyes, the light-sensitive ones not included in the sensitivity range d®r ai © Absorb silver halide radiation.

It is known to produce color photographic images by the silver dye bleaching process. Phot © graphical Mat Riali @ © n _p using werdsn, for this process generally contain red-sensitive Silberhalogenidemulsionsschiehten with a blue-green azo dye, © ine grtixieapfindlieh® silver halide emulsion layer with a purple AsBofarbst®ff and a blue-sensitive with the Gilbert Silbsrhalogenidemuleionssohioht Aeofarbstoff.

00 ^ 885/0518

1622016

A particular advantage of the silver dye bleaching process is in that images with very high lightfastness are obtained. Ba the photosensitive materials contain dyes that in the sensitivity range of the silver halide emulsions containing them absorb, the photographic materials for the silver dye bleaching process are relatively small Sensitivity so that its application is limited to use as a copier material.

Various methods have already been described in order to avoid this disadvantage. Awake a known method colorless hydrazo compounds are used, which after exposure and during photographic processing in an azo dye of the desired color can be transferred. Another known method is to use azo dyes, whose color depends on the pH value. Layers that contain such dyes can, for example, have acidic pH values be adjusted, the absorption of the azo dyes being reversible is shifted into a range which is outside the sensitivity range of the respective silver halide emulsion layer lies. After processing, the pE change receive the desired partial image colors in the layer.

The principle, first of all, dyes in the light-sensitive layers to use that do not absorb in the sensitivity range of the silver halide emulsion and these after

^A - ^g ? ** - -2-. BATH ORIGINAL

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Exposure in the course of the photographic processing of this To convert layers into the final image dyes is in itself quite suitable for solving the problem at hand, since this increases the sensitivity of the layers many times over can be increased. However, the known methods have numerous disadvantages, so that their practical application so far was not possible. These disadvantages consist, for example, in the fact that the original dyes are converted into the final Image dyes run too slowly during photographic processing. In the case of hydrazo compounds, the photographic Properties of the layer adversely affected. The above method in which this reaction results in a pH change is hardly useful for practical purposes because the obtained Color images remain dependent on the pH value, since the conversion reaction is reversible. Fluctuations in the pH value of the air can result in a deterioration in the quality of the final images.

It is an object of the invention to provide a photographic light-sensitive material for the silver dye bleaching process that contains azo dyes that are not in the sensitivity range the silver halide emulsions in which they are contained absorb and which can be converted into image dyes during photographic processing, these transformations proceeding with sufficient speed and must be irreversible.

- ⁷ BAD OFUGiNAL

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It has now become a highly sensitive photographic material found for the silver dye bleaching process that contains at least one silver halide emulsion layer opposite one of the three primary colors of the visible spectrum is sensitive and contains an azo dye whose absorption maximum is is not in the sensitivity range of the emulsion, but is in one during photographic processing the three image dyes can be transferred, these Dyes are characterized in that their auxochromic hydroxyl or amino groups are blocked in such a way that the auxochrome groups during photographic processing by saponification again. Can be set in freedom.

The present invention is based on the principle that the absorption properties can be greatly changed by blocking the auxochrome groups. Becomes the blocking group split off again, the dye with the original properties is created again. In addition, the blocked ones Dyes have a significantly low color intensity.

For the photographic materials of the invention for the Silver dye bleaching processes can use any azo dyes known for this purpose as long as they are one or more carry auxochromic hydroxyl or amino groups. These auxochrome groups are blocked by saponifiable groups.

AG 344 - 4 - ^BATHROOM

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The blocking should be so stable that the blocked Azo dyes in the usual production of photographs Materials cannot be saponified by means of aqueous casting solutions and only after exposure and during the photographic Processing can be saponified. The saponification can take place in the required processing baths, e.g. B. the alkaline Developer, or by means of special baths switched on for this purpose in the processing cycle be performed. After the saponification of the blocking groups, the final image dyes are obtained.

Blocking and saponifiable groups include: the suitable for the following:

-SO ₈ H, -PO ₈ H ₂ , RCO-, RSO ₂ -, -CH ₂ OR, ROCO-, RNHCO-, (CH ₈ ) ₈ Si- or -CH = CH ₂

wherein R is a saturated or unsaturated aliphatic group, preferably with up to 5 carbon atoms or an aromatic, optionally substituted group, preferably phenyl.

As blocked azo dyes that give a yellow image dye, e.g. B. those of the following general formula are suitable: X

/ ~ "Λ- N = NR ¹

\ j * * St "

- I - R ~ in

in

009885/0518
AG 344 - 5 -

where mean:

X = an auxochromic blocked in the manner indicated above

Hydroxyl or amino group; R ¹ = with the remainder of a diazotized or tetrazotized amine

optionally further auxochrome groups; R "= an aliphatic group or aryl, especially phenyl, these groups optionally having further substituents

z. B. may contain water-solubilizing groups. R "'·« hydrogen or R "Dyes suitable for blocking are e.g. B. in the UK Patent documents 918 087, 924 535 or 955 892 or in the deutsohen 740,708.

For the production of the purple-colored part of the picture are the blocked azo dyes of the following general formula:

SO ₅ H where mean:

= Hydrogen, hydroxyl, amino that be acylated, also SuIfο, or sulfonamide, where the sulfonamide group is substituted with alkyl can be;

-6-

009885/0518

Dyes which can be used for blocking are e.g. B. in the UK Patents 1,077,628 or 1,099,335, German patents 1,039,839, 1,039,840 or 1,097,270, and more in the Swiss patent specification 418 128 or the Belgian one Patent 664,755.

As dyes that flen blue-green during processing Image dye, those of the following formula are suitable:

R ^VI - N = N - R ^VI1

- R

^Vm

what mean?

, VII

SO ₅ H

or

SO ₈ H

an optionally substituted arylene group 2 * B. (1) Phenylene, (2) naphthylene, (3) they diphenylene grouping, or (4) a grouping of the following! Formula:

X = a blocked hydroxyl group.

VIII VI
R = R, but with at least one of the two substituents

• represents a naphthalenesulfonic acid grouping *

Dyes suitable for blocking are e.g. B. in the UK

ι, ■

Patents 551 501, 711 232, 939 906, 1 028 562, 1 042 300,

A-B 344

- 7 -

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BATH ORIGINAL

1 045 705, 1 101 215, in German patents 740 708, 1 041 3355 in French patents 956 677, 1 007209 or American patent specification 2,286,714.

The yellow dyes are colorless to in the blocked form very faint yellow. The purple image dyes are colored orange and the cyan image dyes show in the blocked Form a red to purple. Suitable are e.g. B. the

the following dyes:

H ₃ CO

H. C-

N =

NHOC

H ₈ C

CH,

HO ₈ S

CH ₈

v ^Lo p

HO. S.

SO ₈ H

A-G

VNH

CO

SO ₈ H

CO

SO ₈ H

009885/0518

SO ₈ H

O = C

N = N- / \ y_NHO

0 _s H

SO _x H

VNH

O = C

C-I C-O-C

SO ₈ H

^S0 ° ^H

C = O

SO ₈ H

N \ _N = N-C

CH ₈

OH ₈ CO

OCH ₈

7. fv ^Na M ^ - ^il0C -fr ^aHC0H M VOOHH-ZZj

SO ₈ H

SO ₁ H

CH ₈ C = O

-Q 344

SO ₈ H

BAD ORiGJWAL

00988 ^ / 0518

NH ₈ H ₈ CO

N = N. OCO

-NHOCHN.

5 O ₅₅ H.

SO ₅₅ H

OCH,

NH ₂ SO ₈ H

N = NV / \ V_NH0C— // \

.0-SO ₂

'// V-CH _n

SO _x H y-ci ι

Cl

NH, SO ₃ H

10.

SO,

■ ά

COOH

O ₈ H

CO O

Cl

H _S C_ / \\ _ SO _a NH .N = N- / V-NHOC

Y ^

j "SO ₈ H

A-Q - 10 -

BATH

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CH ₈

CH ₈

9 = 0 ο

Cl

HH

CO

^S0 ' ^H

c * o

OCH ₈

0 = (

13. '

OCH ₈

SO * H i,

L /

OC ₈ H ₈ OCH ₈

14th

OCH

SO ₈ H

• SO _x H

A-G 544

-11 -

Ofl988S / 0S18

OC ₂ H ₆

15,

CH,

SO ₃ H SO ₃ H

SO * H

CH _S CH,

16.

OCH ₃ 0 =

OCH,

SO ₃ , H SO, H NHOC-V /

C = O O

OCH ₃ g ⁰

17th

OCH,

NHOCHN- /

SO ₃ H

SO _x H

SO »H SO ₃ H

18 - .V-NHOC-w '/ \

SO ₈ H SO ₈ H

009885/0518

-Q - 12 -

V-SO _n H

The azo dyes on which they are based are known. The production takes place according to known methods, the blocking of the auxochromic groups can also take place in a known manner. One possibility for the blocking is detailed below:
Dye 13

90 parts by weight of the dye of the formula OH OCH,

O = C - // \\ _ SO.H

SO ₃ H

are stirred with 180 parts by weight of benzoyl chloride and 360 parts by volume of pyridine for 3 hours at a bath temperature of 110.degree. After the reaction has ended, most of the pyridine is drawn off and the residue is taken up in 1000 parts by volume of 10% potassium hydrogen carbonate solution. The solution is adjusted to pH 5 with hydrochloric acid and stirred for a few hours; this creates an absorbable shape. The extracted residue was dissolved in 1300 parts of water at 35 ⁰ C with 270 parts by volume of 20 # Kallumhydrogen sodium carbonate solution like. Anso ^ li ^ eiind is stirred well with 900 parts of 3 # sodium chloride solution at 25 ° C , filtered off with suction, rewashed

and dried. Yield about 90 parts by weight. ■ *.

00988570518 A ^ G 344 -

8AD

The blocked azo dyes are used in a known manner. They are of course just as diffusion-resistant as the underlying unblocked dyes. Other required properties such as lightfastness and bleachability are given by the properties of the unblocked dyes that make up the final image dye.

The photographic materials of the present invention show due the permeability of the azo dyes present in the layer is in the sensitivity range of the silver halide emulsion layers about 5 to 10 times higher sensitivity compared to the same layers, which, however, instead of the blocked ones Contain dyes the underlying unblocked. The photographic materials of the invention can therefore be used as a recording material.

The photographic materials of the invention can be according to exposed to a simple black-and-white negative development and then subjected to direct positive dye images in the usual way are processed.

However, black and white reversal development can also be carried out and then, after going through the treatment baths of the silver dye bleaching process, obtains dye images with a zur Submission of opposing gradation, as it is based on the production of positive, colored reflective and transparent images

A-G 34-4. - 14- - * —— * *

^ ² * BAD OBiGfMAL

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of color negatives are desired.

The blocked dyes are largely inert to the usual ones Amounts of emulsion additives such as stabilizers, plasticizers, wetting agents, hardeners and other substances, z. B. added sensitizers.

The dyes to be used in the manner according to the invention are conventionally converted into silver halide emulsions which Silver chloride, bromide or mixtures thereof, possibly together with silver iodide, are added. Color photography marriage Layers made with them can be applied to any type of substrate made of paper, baryta-coated paper, or polyethylene-laminated paper Paper, polypropylene-coated or otherwise hydrophobized Paper, glass, metallized foils of all kinds, cellulose acetates in transparent or pigmented form be potted, as well as on subbed, transparent or pigmented foils made of polyester etc.

The blocking group which changes the absorption properties of the azo dyes is in most cases saponified without difficulty in an alkaline developer bath. The composition of the developer bath generally does not need to be changed. Slight changes in terms of both the development and the saponification of the blocking group can be determined without difficulty by a few manual tests .

-S 344 - 15 - _BÄD ORIGINAL

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In a few cases it may be advisable to use a special saponification bath to switch to the processing step. This can happen before or after the initial development. Suitable as saponification baths are aqueous alkaline baths with a pH value between 9 and 14 for the saponification of acyl groups. if the blocking group is bound to the dye molecule by an ether bond, acidic saponification baths are preferable. These are aqueous baths with a pH value between 0 and 4. The saponification baths can optionally Contains wetting agents.

The remainder of the processing step, in particular the bleaching of the dye, is carried out in the usual way, e.g. B. with those based on quinoline and iodide or on thiourea and various bleach catalysts such as quinoline, quinoxazoline derivatives and the like

example 1

6.5 g of a dye of the formula No. 13 are dissolved in 400 ml of water and added to 800 ml of an aurgescnmolten roxsensiDilized silver bromide gelatin emulsion. After adding 20 ml of a 1 # aqueous solution of N, N ¹ , N "-trisacryloylhydrotriazine-1,3,5 as hardening agent, it is poured onto a layer of pigmented cellulose triacetate in a layer thickness of about 5 nm, which is an application of Ag of 0.8 - 1.3 g Ag / m.

00988 570518

A strip of the unexposed material will be in an acidic Fixing bath fixed. Another strip is exposed to red light in a conventional sensitometer behind a step wedge and processed as follows:

1. development; 5 minutes in

p-methylaminophenol

Hydroquinone

Sodium sulfate

NaBr

soda

Water on

1 g

3 g

13 g

1 g 26 g ml

2. watering; 5 minutes

3. hardening; 5 minutes in

Formalin ($ 30) soda
.Water on

4. watering; 5 minutes

5. Color bleaching in 15 minutes

Potassium iodide
Sodium hypophosphite, sulfuric acid, conc., Quinoline

Water on
<■

6. Soak: 5 minutes

ml 20 g ml

10 g 5 g 75 ml 50 ml 1000 ml

BATH ORIGINAL

A-G

098185/0518

7. Bleach-fix: 10 minutes in

Tetrasodium ethylenediamine tetracetate 26 g

Soda sicc. 24 g

Iron-3-chloride. 15 g

Sodium sulfite sicc. 13 g

Sodium thiosulfate 200 g

Water to 800 ml

8. Soak: 15 minutes

After drying, a blue-green dye wedge is obtained Brilliance with good whites.

The absorption properties of the processed sample, and the only fixed comparison sample are compared in the following tab ^:

Density wavelength comparison sample processed sample

680 nm 0.4 2.7

660 0.6 3.1

640 1.2 3.5

620 1.7 3.4

600 2.1 2.8

580 2.7 2.1

560 ■ 2.8 1.2

540 3.0 0.6

520 2.7 x 0.4

As the table shows, the density of the dye used is in the range of 640 - 700 nm before processing in which the emulsion is sensitized, only a fraction the density after processing, so that a considerable gain in sensitivity can be achieved.

00 98 8 5/0518

AG 344 - ^

Example 2

5.5 g of the dye of the formula No. 19 are dissolved in 400 ml of water and added to 800 ml of a red-sensitized silver bromide emulsion. After adding 20 ml of a 1- follow aqueous solution of 2 ^ -o-trisacryloyltriazine-l ^, 5 it is poured onto a layer support made of cellulose triacetate with a layer thickness that corresponds to an Ag application of 0.8-1.3 g Ag / m is equivalent to.

The procedure is as indicated in Example 1, but the processed step wedge is then treated with 0.5 η for a further 5 minutes NaOH and then water out well. A blue-green color wedge with good whites is obtained. The absorption properties before and after processing result from the following table:

Density wavelength comparison sample processed sample

680 nm 0.03 1.00

660 0.06 0.90

640 0.11 0.70

620 0.23 0.54

600 0.29 0.36

580 0.31 0.26

560 0.32 0.19

540 0.32 0.16

520 0.31 0.16

Example 3

7.5 g of the dye of the formula No. 6 are dissolved in 500 ml of water and added to 850 ml of a green-sensitized silver bromide emulsion . After adding 20 ml of a 1 % aqueous solution of 2 ^ -ö-Trisacryloyltriazin-l ^^ one pours on a layer support made of cellulose triacetate in a layer thickness that

AG 344 - 19 - ^ßAU ORiiSli ^ -.

009885/0518

corresponds to an Ag application of 0.8 - 1.3 g Ag / m. One moves as indicated in Example 2 and is given a purple color wedge with good whites. The absorption properties before and after processing, the following table shows:

Density wavelength comparison sample processed sample

400 0.86 0.27

440 0.70 0.39

480 0.53 0.75

520 0.31 1.13

560 0.21 0.74

600 0.13 0.40

L-G 344 - 20 -

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Claims (1)

.ΊΒ2Υ9Ί6 • Μ Claims 1. Photographic light-sensitive material for the Silver dye bleaching process with at least one silver halide emulsion layer which is opposite to one of the three basic colors of the visible spectrum is sensitive and which contains a dye whose absorption maximum is not in the sensitivity range of the emulsion, but which converts into one of the three image dyes during photographic processing can be, characterized in that the dye is an azo dye whose auxochromic hydroxyl or amino groups are blocked in such a way that the auxochrome groups are saponified during photographic processing can be set free again. / 2ß Photosensitive material according to claim 1, characterized in that the auxochromic group "are blocked by one of the following saponifiable groups: -SO ₉ H, -PO ₃ H ₂ , RCO-, RSO ₂ -, -CH ₂ OR, ROCO-, RNHCO-, (CHa) ₈ Si- or -CH = CH ₂ wherein R is a saturated or unsaturated aliphatic group or represents an aromatic optionally substituted group. 3. Photosensitive material according to claim 2 with a blue-sensitive silver halide emulsion layer, characterized AG 344 - 21 - 009885/0518 indicates that this layer contains an azo dye of the following formulas: N = Ii - R ¹ II R ^1L - N JN = N - R III R ¹¹ C-N = N-R ¹ 0 = where mean: X = a blocked auxochromic hydroxyl group A ι og; -uppej R = the remainder of a diazotized or tetr .erten amine with possibly further auxochromes' .jippej; R = an ÄLiphatic group or aryl, wooe ,. these graps may optionally contain further substituents. R ¹¹¹ = hydrogen or R ¹¹ 4. Photographic light-sensitive material according to claim 2, with a green sensitive silver hebgenide emulsion layer, thereby characterized in that this layer contains a blocked azo dye of the following formula: 0098857 # §Γ8 SO ₃ H where mean: R = the remainder of a diazotized or tetrazotized amine with optionally further auxochromic groups; ' R = an aliphatic ^ group or aryl, these groups may optionally contain further substituents. R ¹¹¹ = hydrogen or R ¹¹
R » hydrogen, hydroxyl, amino, as aoylitrt can be, sulpho or sulfonamidj V - R ^IV 5. A photographic light-sensitive material according to claim 2 having a red-sensitive silver halide emulsion layer, thereby characterized in that this layer contains an azo dye of the following formula: R ^VI - N = N τ R ^VI1 - N = N - R ^VI11 where mean: or SO ₃ H A-G 344 BATH ORIGINAL R = an optionally substituted arylene group j VIII VI R = R, but with at least one of the two substituents represents a naphthallic sulfonic acid group! X = a blocked hydroxyl group. 6. Photographic light-sensitive material according to claim 5, VII characterized in that R is phenylene, naphthylene, a diphenyl grouping or a grouping of the following formula j « means. AG 344 - 24 - 009885/0518